Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

• the present invention relates to a free-flowing particulate detergent composition, or component therefor, containing crystalline alkali metal aluminosilicate (zeolite) and also including a liquid, viscous-liquid, oily or waxy detergent ingredient.
• zeolite crystalline alkali metal aluminosilicate
• crystalline alkali metal aluminosilicate zeolite
• Particulate detergent compositions containing zeolite are widely disclosed in the art, for example, in GB 1 473 201 (Henkel), and are sold commercially in many parts of Europe, Japan and the United States of America.
• Zeolite A has the advantage of being a "maximum aluminium" structure containing the maximum possible proportion of aluminium to silicon - or the theoretical minimum Si:Al ratio of 1.0 - so that its capacity for taking up calcium ions from aqueous solution is intrinsically greater than those of zeolite X and P which generally contain a lower proportion of aluminium (or a higher Si:Al ratio).
• EP 384 070A (Unilever) describes and claims a novel zeolite P (maximum aluminium zeolite P, or zeolite MAP) having an especially low silicon to aluminium ratio, not greater than 1.33 and preferably not greater than 1.15. This material is demonstrated to be a more efficient detergency builder than conventional zeolite 4A.
• US 3 112 176 (Haden et al/Minerals & Chemicals Philipp Corporation) relates to the preparation, from metakaolin, of a novel zeolite having a silicon to aluminium ratio of approximately 1:1, an exceptionally high base exchange capacity, and a very high oil absorption capacity.
• the zeolite is defined by an X-ray diffraction pattern which is that characteristic of zeolite P.
• the material contains a relatively high level of titanium impurity (derived from the metakaolin starting material). Suggested uses are for water treatment in the chemical industry and in sugar production, and as a pigment or filler in the production of plastics and rubber goods.
• zeolite A in detergent compositions as a carrier for liquid ingredients such as nonionic surfactants
• GB 1 504 211 Henkel
• EP 149 264A Unilever discloses a spray-dried granular material, based on zeolite A, for carrying large loadings of liquid, viscous-liquid, oily or waxy detergent components, for example nonionic surfactants: the resulting "adjuncts" are free-flowing powders.
• zeolite MAP both in powder form and when granulated with or without other materials, is substantially superior to zeolite A as a carrier for liquid, viscous-liquid, oily or waxy detergent ingredients such as nonionic surfactants, allowing the preparation of stable free-flowing powders containing high proportions of such ingredients.
• EP 448 297A (Unilever), published on 25 September 1991, discloses a laundry detergent composition containing a detergency builder comprising zeolite MAP and a citrate.
• the compositions may contain nonionic surfactants.
• a detergency builder composition containing zeolite MAP and citrate which may also contain nonionic surfactant as a binder.
• the present invention provides the use of zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP) as a carrier for liquid, viscous-liquid, oily or waxy detergent ingredients in a free-flowing particulate detergent composition or component therefor comprising
• the invention also provides a free-flowing particulate detergent composition or component therefor, which comprises
• the invention further provides a free-flowing particulate detergent composition or component therefor, which comprises
• the invention still further provides a free-flowing particulate detergent composition or component therefor, which comprises
• the subject of the invention is a free-flowing particulate composition which may be a complete detergent product in its own right, or a component of a more complex product.
• the invention arises from the observation that the absorption and carrying capacity of zeolite MAP for liquid, viscous-liquid, oily or waxy ingredients is unexpectedly good compared with that of zeolite A.
• composition or component of the invention has two essential ingredients: the particulate carrier material (i), and the adsorbed liquid, viscous-liquid, oily or waxy ingredient (ii) carried.
• Other detergent ingredients may also be present if required or desired.
• the ratio of the ingredient (ii) to the zeolite MAP is at least 0.01:1, preferably from 0.01:1 to 1.4:1, and may advantageously lie within the range of from 0.01:1 to 0.75:1. It is preferably at least 0.1:1, and advantageously at least 0.35:1, more advantageously at least 0.45:1, and may be as high as 1:1 or even 1.4:1; but compositions having lower ratios that do not utilise the full carrying capacity of zeolite MAP are also within the scope of the invention. The ratio most preferably lies within the range of from 0.1:1 to 1:1.
• compositions and components in accordance with the invention suitably contain from 2 to 45 wt% of the ingredient (ii), based on the total of the particulate carrier material (i) and the ingredient (ii).
• the particulate carrier material is selected from the particulate carrier material
• the particulate carrier material consists wholly or partially of zeolite MAP.
• Zeolite MAP maximum aluminium zeolite P
• EP 384 070A Unilever
• It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range of from 0.9 to 1.33, and more preferably within the range of from 0.9 to 1.2.
• zeolite MAP having a silicon to aluminium ratio not greater than 1.15; and zeolite MAP having a silicon to aluminium ratio not greater than 1.07 is especially preferred.
• Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilicate, as measured by the standard method described in GB 1 473 201 (Henkel) and also described, as "Method I", in EP 384 070A (Unilever).
• the calcium binding capacity is normally at least 160 mg CaO/g and may be as high as 170 mg CaO/g.
• Zeolite MAP also generally has an "effective calcium binding capacity", measured as described under "Method II" in EP 384 070A (Unilever), of at least 145 mg CaO/g, preferably at least 150 mg CaO/g.
• zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are generally expressed in terms of the notional anhydrous material.
• the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is normally about 20 wt%.
• Preferred zeolite MAP for use in the present invention is especially finely divided and has a d 50 (as defined below) within the range of from 0.1 to 5.0 micrometres, more preferably from 0.4 to 2.0 micrometres and most preferably from 0.4 to 1.0 micrometres.
• the quantity “d 50 " indicates that 50 wt% of the particles have a diameter smaller than that figure, and there are corresponding quantities "d 80 ", "d 90 " etc.
• Especially preferred materials have a d 90 below 3 micrometres as well as a d 50 below 1 micrometre.
• the zeolite MAP may have not only a small average particle size, but may also contain a low proportion, or even be substantially free, of large particles.
• the particle size distribution may advantageously be such that at least 90 wt% and preferably at least 95 wt% are smaller than 10 micrometres; at least 85 wt% and preferably at least 90 wt% are smaller than 6 micrometres; and at least 80 wt% and preferably at least 85 wt% are smaller than 5 micrometres.
• the carrier material is simply zeolite MAP in powder form which has a d 50 within the range of 0.4 to 1.0 micrometres.
• Powdered zeolite MAP has been found to be an excellent carrier material: for example, the amount of mineral oil (g per g anhydrous zeolite) that it can take up before losing its free-flowing character is has been found to be from 1.2 to 1.9 times as great as the corresponding amount for commercial zeolite A powders.
• detergent ingredients in powder form may be present in admixture with the zeolite MAP powder.
• the particle size of zeolite MAP powder is small, and the material may be more conveniently handled if granulated, by spray-drying or by a non-tower method, to form larger particles.
• Granular materials of this type based on zeolite A are well-known and are sold commercially, for example, as Wessalith (Trade Mark) CS and CD by Degussa AG, Germany.
• the carrier material is a granulate comprising from 10 to 80 wt%, preferably from 50 to 80 wt%, of zeolite MAP.
• the second embodiment of the invention encompasses granular carrier materials prepared by non-tower processes such as dry mixing and granulation.
• compositions according to the first and second embodiments of the invention may then be prepared by treating the carrier material (powder or granulate), for example, by spraying, with one or more liquid, viscous-liquid, oily or waxy detergent ingredients.
• the carrier material for example, by spraying
• Such compositions will generally be components of more complex products, rather than whole detergent products in their own right.
• the zeolite MAP may also be incorporated in a detergent base powder containing detergent-active materials, and optionally other compatible ingredients such as supplementary builders, sodium silicate, fluorescers, and antiredeposition polymers.
• a detergent base powder containing detergent-active materials, and optionally other compatible ingredients such as supplementary builders, sodium silicate, fluorescers, and antiredeposition polymers.
• Such a base powder may be prepared by spray-drying, but non-tower methods such as dry mixing or granulation are also possible.
• the amount of zeolite MAP in the base powder may suitably range from 10 to 80 wt%.
• the base powder may then be treated, for example, by spraying, with one or more liquid, viscous-liquid, oily or waxy detergent ingredients.
• the resulting particulate composition may represent a fully formulated detergent composition; or, if desired, further particulate ingredients may then be admixed (postdosed), in the conventional manner, to arrive at the final product.
• a third embodiment of the invention which may be regarded as a variation of the first embodiment, is a particulate material of high bulk density prepared in a high-speed mixer/granulator.
• zeolite MAP generally in powder form
• the liquid, viscous-liquid, oily or waxy detergent ingredient are mixed and granulated, optionally together with other ingredients, in a high-speed mixer/granulator, to give an agglomerate of high bulk density.
• binders include polycarboxylate polymers, for example, polymers of acrylic and/or maleic acid, in aqueous solution; and aqueous solutions of inorganic salts, for example, sodium carbonate or sodium silicate.
• Detergent-active compounds may also act as binders; and some compositions will already contain ingredients, such as detergent-active compounds, that will render the addition of further binders unnecessary. Additional water may be needed to bring about agglomeration, and a subsequent drying step may also be required.
• the product may suitably contain from 20 to 80 wt% of zeolite MAP, from 15 to 40 wt% of the liquid, viscous-liquid, oily or waxy detergent ingredient, and binder, water and optionally other ingredients to 100 wt%.
• the process may be carried out in a high-speed batch mixer/granulator having both a stirring action and a cutting action, as described and claimed in EP 340 013A (Unilever).
• a high-speed batch mixer/granulator having both a stirring action and a cutting action, as described and claimed in EP 340 013A (Unilever).
• the stirrer and the cutter may be operated independently of one another, and at separately variable speeds.
• Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. It is thus a highly versatile and flexible piece of apparatus.
• a preferred type of batch high-speed mixer/granulator is bowl-shaped and preferably has a substantially vertical stirrer axis.
• mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
• the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
• the Fukae mixer requires batch operation.
• continuous processes may be employed, for example, using a continuous high-speed mixer/granulator such as the Lödige (Trade Mark) Recycler, optionally followed by a moderate-speed continuous mixer/granulator such as the Lödige Ploughshare.
• Suitable processes are disclosed in EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
• the high-speed mixer/granulator is used to effect in-situ neutralisation of an acid precursor of an anionic surfactant, for example, linear alkylbenzene sulphonic acid or a primary alcohol sulphuric acid, with a solid mixture including a neutralising alkaline salt (for example, sodium carbonate) and zeolite MAP.
• an anionic surfactant for example, linear alkylbenzene sulphonic acid or a primary alcohol sulphuric acid
• a solid mixture including a neutralising alkaline salt for example, sodium carbonate
• zeolite MAP zeolite MAP
• the granulate obtained typically has a bulk density of at least 700 g/litre. It may be used as a complete detergent composition in its own right, or may be admixed with other components or mixtures prepared separately to form a major or minor part of a final product.
• liquid, viscous-liguid, oily, or waxy detergent ingredient The liquid, viscous-liguid, oily, or waxy detergent ingredient
• the ingredient is a detergent-active compound (surfactant), which may be anionic, nonionic, zwitterionic, amphoteric or cationic.
• surfactant may be anionic, nonionic, zwitterionic, amphoteric or cationic.
• the invention is especially useful for the incorporation of fluid or mobile surfactants or surfactant mixtures into detergent powders. It has been found of particular value for incorporating high levels of mobile nonionic surfactants, or mobile mixtures of anionic and nonionic surfactants, into detergent powders.
• Nonionic surfactants are well-known in the art. Ethoxylated nonionic surfactants are especially preferred. Suitable examples include C 10 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol; more especially, the C 12- C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. The alcohols having an average degree of ethoxylation below 10 are more mobile than the more highly ethoxylated materials and they benefit particularly from the present invention.
• the invention is also applicable to nonionic surfactants other than ethoxylates, for example, alkylpolyglycosides; O-alkanoyl glucosides as described in EP 423 968A (Unilever); and alkyl sulphoxides as described in our copending British Patent Application No. 91 16933.4.
• nonionic surfactants other than ethoxylates, for example, alkylpolyglycosides; O-alkanoyl glucosides as described in EP 423 968A (Unilever); and alkyl sulphoxides as described in our copending British Patent Application No. 91 16933.4.
• An especially preferred liquid, viscous-liquid, oily, or waxy detergent ingredient that can be used in the present invention is a mixture of an ethoxylated nonionic surfactant with a primary or secondary alcohol sulphate.
• the liquid, viscous-liquid, oily or waxy ingredient may also be an acid precursor of an anionic surfactant, for example, linear alkylbenzene sulphonic acid.
• an anionic surfactant for example, linear alkylbenzene sulphonic acid.
• neutralisation normally accompanies mixing, granulation or other process steps so that the final product contains the surfactant in neutralised, salt form.
• compositions of the invention have excellent flow properties even with very high proportions of liquid, viscous-liquid, oily or waxy ingredient.
• powder flow is defined in terms of the dynamic flow rate, in ml/s, measured by means of the following procedure.
• the apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm.
• the tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm.
• a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
• the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
• the averaging and calculation are carried out electronically and a direct read-out of the DFR value obtained.
• compositions and components of the present invention generally have dynamic flow rates of at least 90 ml/s, preferably at least 100 ml/s.
• the carrier materials used in accordance with the invention not only have a larger capacity than similar materials based on zeolite A for taking up liquid ingredients such as nonionic surfactants; they also exhibit reduced leakage or bleeding out of such ingredients during storage. In a detergent powder, bleeding of mobile ingredient such as nonionic surfactant can lead to pack penetration, giving internal and external staining of the pack, which is highly undesirable.
• Particulate compositions of the invention may form the whole, or a major or minor part, of a detergent composition.
• Fully formulated detergent compositions in accordance with the invention may contain any suitable ingredients normally encountered, for example, detergent-active compounds (surfactants) which may be anionic, nonionic, cationic, amphoteric or zwitterionic; fatty acid soaps; organic or inorganic builder salts in addition to zeolite MAP, including other zeolites such as A or X; other inorganic salts such as sodium silicate and sodium sulphate; antiredeposition agents such cellulose derivatives and acrylic/maleic polymers; fluorescers; bleaches, bleach precursors, and bleach stabilisers; enzymes; dyes; coloured speckles; and perfumes.
• surfactants may be anionic, nonionic, cationic, amphoteric or zwitterionic
• fatty acid soaps organic or inorganic builder salts in addition to zeolite MAP, including other zeolites such as A or X; other inorganic salts such as sodium silicate and sodium sulphate; antirede
• the zeolite MAP used in the Examples was prepared by a method similar to that described in Examples 1 to 3 of EP 384 070A (Unilever). Its silicon to aluminium ratio was 1.07. Its particle size (d 50 ) as measured by the Malvern Mastersizer was 0.8 micrometres.
• zeolite A used was Wessalith (Trade Mark) P powder ex Degussa.
• nonionic surfactants used were Synperonic (Trade Mark) A7 and A3 ex ICI, which are C 12 -C 15 alcohols ethoxylated respectively with an average of 7 and 3 moles of ethylene oxide.
• the acrylic/maleic copolymer was Sokalan (Trade Mark) CP5 ex BASF.
• the zeolite A materials were as follows: Example Trade name Manufacturer A Wessalith P Degussa B Doucil P Crosfield C Birac Birac D Soprolit Montedison E IZL Industrial Zeolites
• Detergent base powders were prepared to the following formulations (in weight percent) by spray-drying aqueous slurries: 2 F Linear alkylbenzene sulphonate 12.20 12.20 Nonionic surfactant 7EO 5.60 5.60 Soap 3.40 3.40 Zeolite 4A (as anhydrous) - 36.40 Zeolite MAP (as anhydrous) 36.40 - Acrylic/maleic copolymer 5.50 5.50 Sodium alkaline silicate 0.80 0.80 Sodium carbonate 22.10 22.10 SCMC 1.00 1.00 Fluorescer 0.40 0.40 Moisture (nominal) 12.40 12.40 100.00 100.00 100.00
• Nonionic surfactant added g
• % nonionic surfactant (on product) nonionic surfactant zeolite (anh) ratio dynamic flow rate (ml/s) 2 F 0 0 - 120 121 10 3.85 0.11 114 83 15 5.66 0.16 - 69 20 7.41 0.22 111 23 25 9.09 0.27 103 - 30 10.71 0.33 101 - 35 12.28 0.38 98 - 40 13.79 0.44 97 - 45 15.25 0.49 94 - 50 16.67 0.55 99 - 55 18.03 0.60 23 -
• Example 2 was repeated using powders containing higher proportions of zeolite.
• the formulations were as follows: 3 G Linear alkylbenzene sulphonate 10.30 10.30 Nonionic surfactant 7EO 4.70 4.70 Soap 2.80 2.80 Zeolite 4A (as anhydrous) - 43.10 Zeolite MAP (as anhydrous) 43.10 - Acrylic/maleic copolymer 4.60 4.60 Sodium alkaline silicate 0.70 0.70 Sodium carbonate 18.70 18.70 SCMC 0.90 0.90 Fluorescer 0.30 0.30 Water (nominal) 13.90 13.90 100.00 100.00
• Nonionic surfactant added g
• % nonionic surfactant (on product) nonionic surfactant zeolite (anh) ratio dynamic flow rate (ml/s) 3 G 0 0 - 122 120 28 10.07 0.23 - 82 36 12.59 0.33 118 83 40 13.79 0.37 114 86 44 14.97 0.41 114 55 60 19.35 0.56 112 - 68 21.38 0.63 107 - 76 23.17 0.71 24 -
• Detergent base powders of high bulk density were prepared by granulating and densifying the spray-dried base powders of Examples 3 and G using a Fukae (Trade Mark) FS-30 high-speed mixer/granulator, in the presence of nonionic surfactant (3EO).
• the mixer was operated at a stirrer speed of 200 rpm and a cutter speed of 3000 rpm, the temperature being controlled at 60°C by means of a water jacket; the granulation time was 2 minutes. The amount of nonionic surfactant added was adjusted to give satisfactory granulation.
• Powders of high bulk density having the formulations given below (in weight percent) were prepared by a non-tower process using the Fukae (Trade Mark) FS-30 high-speed mixer/granulator.
• Fukae Trade Mark
• FS-30 high-speed mixer/granulator.
• Nonionic surfactant 7EO 24.05 20.55 Water 6.33 4.11 100.00 100.00
• the zeolite powder was first added to the mixer/granulator, then the aqueous polymer solution and liquid nonionic surfactant were added with the stirrer rotating at 100 rpm and the cutter at 3000 rpm.
• the temperature of the equipment was controlled to 25°C by means of a water jacket.
• the quantity of water required to effect agglomeration was then added, and the mixer was operated with the stirrer rotating at 200 rpm and the cutter at 3000 rpm. The time required in each case was 1.5 minutes.
• the test used gives an estimate of the degree of bleeding during a three week storage period at 37°C by measuring the amount of nonionic surfactant absorbed by preweighed filter papers placed near the top and bottom of a powder column.
• a 400 g sample of each powder was weighed out. Powder was poured to a depth of 1 cm into the base of a cylindrical container of diameter 15 cm, and an accurately weighed filter paper (Schleicher and Schull No. 589) placed on top of the powder. More powder was added to an approximate depth of 5 cm above the filter paper, and then covered with a second accurately weighed filter paper. The remainder of the powder sample was then used to cover the second filter paper.
• the container was tightly sealed and stored in a dry atmosphere at 37°C for 3 weeks. After the storage period the filter papers were removed and weighed, the increase in weight of each calculated, and the values for the two increases averaged.
• the powders tested were all prepared by granulation in the Fukae mixer as described in Example 5.
• the nonionic surfactant was Synperonic A3. Amounts are in parts by weight.
• Nonionic surfactant 3EO 17 17 17 Ratio nonionic:zeolite 0.53 0.53 0.53 Increase in weight of filter paper (g) 88 59 57
• Example 6 Using zeolite 4A, it was necessary to include sodium carbonate in order to achieve successful granulation (Comparative Example K), whereas with the same amount of zeolite MAP no sodium carbonate was required (Example 6). Comparison of Examples 6 and 7 show that sodium carbonate had little or no effect on bleeding, so that it was not the absence of sodium carbonate that was responsible for the better results obtained with zeolite MAP.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=10697275

Family Applications (1)

Country Status (20)

Families Citing this family (27)

Family Cites Families (20)

• 1991
  • 1991-06-25 GB GB919113675A patent/GB9113675D0/en active Pending
• 1992
  • 1992-06-12 MY MYPI92001197A patent/MY106931A/en unknown
  • 1992-06-18 DE DE69232364T patent/DE69232364T2/de not_active Expired - Lifetime
  • 1992-06-18 EP EP92305590A patent/EP0521635B1/en not_active Expired - Lifetime
  • 1992-06-18 ES ES92305590T patent/ES2170749T3/es not_active Expired - Lifetime
  • 1992-06-19 CA CA002071745A patent/CA2071745C/en not_active Expired - Lifetime
  • 1992-06-22 NZ NZ243249A patent/NZ243249A/en not_active IP Right Cessation
  • 1992-06-23 PH PH44550A patent/PH31613A/en unknown
  • 1992-06-24 PL PL92295004A patent/PL174152B1/pl unknown
  • 1992-06-24 KR KR1019920010995A patent/KR960001011B1/ko not_active Expired - Fee Related
  • 1992-06-24 AU AU18503/92A patent/AU660466B2/en not_active Expired
  • 1992-06-24 BR BR929202394A patent/BR9202394A/pt not_active IP Right Cessation
  • 1992-06-24 CZ CS921951A patent/CZ280366B6/cs not_active IP Right Cessation
  • 1992-06-24 HU HU9202101A patent/HU216715B/hu unknown
  • 1992-06-24 IN IN200BO1992 patent/IN176371B/en unknown
  • 1992-06-24 SK SK1951-92A patent/SK278646B6/sk not_active IP Right Cessation
  • 1992-06-25 JP JP4167958A patent/JPH0739594B2/ja not_active Expired - Fee Related
  • 1992-06-25 ZA ZA924708A patent/ZA924708B/xx unknown
  • 1992-07-27 SA SA92130031A patent/SA92130031B1/ar unknown
• 1995
  • 1995-08-11 US US08/514,475 patent/US5518649A/en not_active Expired - Lifetime

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events